Substituent Effects on Ni S Bond Dissociation Energies and … · 2012-03-30 · Substituent Effects on Ni−S Bond Dissociation Energies and Kinetic Stability of Nickel Arylthiolate

S1

Supporting Information

Substituent Effects on Ni−S Bond Dissociation Energies and Kinetic Stability of Nickel Arylthiolate Complexes Supported by a Bis(phosphinite)-Based Pincer Ligand

Jie Zhang, Anubendu Adhikary, Krista M. King, Jeanette A. Krause and Hairong Guan*

Department of Chemistry, University of Cincinnati, P. O. Box 21072, Cincinnati, Ohio 45221-0172, United States

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ORTEP drawings of nickel thiolate complexes 1b, 1d, 1e, and 2a-e

S2-S7

Summary of crystallographic data for the nickel thiolate complexes !

S8

Selected bond lengths and angles for the nickel thiolate complexes S9

Kinetics data for the reaction between complexes 1a-e and benzyl bromide !

S10-S13

Hammett plot for the reaction between complexes 1a-e and benzyl bromide

S14

Kinetics data for the reaction between 2a (and 2c) and benzyl bromide! S14-S15 !

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Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2012

S2

Fig. S1 ORTEP drawing of [2,6-(Ph2PO)2C6H3]NiSC6H4CH3 (1b) at the 50% probability level.

Hydrogen atoms are omitted for clarity.

Fig. S2 ORTEP drawing of [2,6-(Ph2PO)2C6H3]NiSC6H4Cl (1d) at the 50% probability level.



S3

Fig. S3 ORTEP drawing of [2,6-(Ph2PO)2C6H3]NiSC6H4CF3 (1e) at the 50% probability level.

Hydrogen atoms are omitted for clarity. The F-atoms of the CF3 group are disordered; a two-

component model is given (70 : 30 occupancy).


S4

Fig. S4 ORTEP drawing of {2,6-[(i-Pr)2PO]2C6H3}NiSC6H4OCH3 (2a) at the 50% probability

level. Hydrogen atoms are omitted for clarity.


S5

Fig. S5 ORTEP drawing of {2,6-[(i-Pr)2PO]2C6H3}NiSC6H4CH3 (2b) at the 50% probability


Fig. S6 ORTEP drawing of {2,6-[(i-Pr)2PO]2C6H3}NiSPh (2c) at the 50% probability level.



S6

Fig. S7 ORTEP drawing of {2,6-[(i-Pr)2PO]2C6H3}NiSC6H4Cl (2d) at the 50% probability level.



S7

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Fig. S8 ORTEP drawing of {2,6-[(i-Pr)2PO]2C6H3}NiSC6H4CF3 (2e) at the 50% probability



S8 Table S1 Sum

mary of crystallographic data

1b

1d 1e

2a 2b

2c 2d

2e

empirical form

ula

C37 H

30 O2 P

2 SNi

C36 H

27 ClO

2 P2 SN

i C

37 H27 F

3 O2 P

2 SNi

C25 H

38 O3 P

2 SNi

C25 H

38 O2 P

2 SNi

C24 H

36 O2 P

2 SNi

C24 H

35 O2 P

2 SClN

i C

25 H35 F

3 O2 P

2 SNi

formula w

eight 659.32

679.74 713.30

539.26 523.26

509.24 543.68

577.24 tem

p, K

150(2) 150(2)

150(2) 150(2)

150(2) 150(2)

150(2) 150(2)

crystal system

monoclinic

monoclinic

monoclinic

monoclinic

triclinic m

onoclinic triclinic

triclinic space group

P21 /n

P21 /n

P21 /n

C2/c

P-1 P2

1 /c P-1

P-1 a, Å

14.8305(4)

14.7575(3) 15.0497(4)

36.0524(10) 10.2691(2)

7.8432(1) 8.5017(2)

8.6345(1) b, Å

9.1267(2)

9.1218(2) 9.1562(2)

7.6168(2) 11.3934(2)

31.3580(5) 9.6113(2)

9.6238(2) c, Å

24.2462(6)

24.1885(5) 24.2103(6)

25.0220(8) 13.1019(2)

10.3910(2) 16.6023(4)

16.8946(3) α, deg

90 90

90 90

88.437(1) 90

85.405(1) 84.721(1)

β, deg 105.642(1)

105.398(1) 104.941(1)

129.255(3) 67.681(1)

94.459(1) 78.043(1)

79.927(1) γ, deg

90 90

90 90

66.738(1) 90

88.327(1) 88.646(1)

Volum

e, Å3

3160.27(13) 3139.25(11)

3223.34(14) 5320.6(3)

1289.15(4) 2547.90(7)

1322.80(5) 1376.34(4)

Z 4

4 4

8 2

4 2

2 d

calc , g/cm3

1.386 1.438

1.470 1.346

1.348 1.328

1.365 1.393

λ, Å

1.54178 1.54178

1.54178 1.54178

1.54178 1.54178

1.54178 1.54178

µ, mm

-1 2.714

3.516 2.846

3.109 3.160

3.184 4.009

3.177 no. of data collected

26302 26034

26573 21489

11035 21765

11430 11813

no. of unique data 5650

5630 5601

4603 4444

4588 4586

4754 R

int 0.0622

0.0335 0.0731

0.0356 0.0288

0.0347 0.0225

0.0298 G

oodness-of-fit on F2

1.024 1.043

1.024 1.033

1.032 1.033

1.050 1.019

R1, w

R2 (I > 2σ(I))

0.0390, 0.0987 0.0322, 0.0851

0.0493, 0.1165 0.0321, 0.0838

0.0377, 0.0957 0.0344, 0.0867

0.0341, 0.0878 0.0407, 0.1020

R1, w

R2 (all data)

0.0519, 0.1069 0.0374, 0.0888

0.0746, 0.1306 0.0379, 0.0876

0.0477, 0.1019 0.0414, 0.0916

0.0402, 0.0922 0.0526, 0.1092

!!!


S9

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Table S2 Selected bond lengths (Å

) and angles (deg)

1b

1d 1e

2a 2b

2c 2d

2e

Ni−S1

2.1947(7) 2.1961(5)

2.2030(10) 2.2191(6)

2.1908(7) 2.1734(6)

2.2083(6) 2.2075(8)

Ni−C

1 1.907(2)

1.9088(17) 1.910(3)

1.8988(19) 1.907(2)

1.8987(19) 1.900(2)

1.899(3) N

i−P1 2.1555(7)

2.1569(5) 2.1595(10)

2.1769(6) 2.1566(7)

2.1507(6) 2.1736(6)

2.1476(8) N

i−P2 2.1452(7)

2.1472(5) 2.1504(10)

2.1377(6) 2.1538(7)

2.1625(6) 2.1472(6)

2.1740(8) S1−C

31 1.784(3)

1.7800(19) 1.781(4)

1.766(2) 1.789(3)

1.775(2) 1.767(2)

1.768(3) P1−O

1 1.6592(17)

1.6593(13) 1.661(2)

1.6612(14) 1.6572(17)

1.6627(14) 1.6614(15)

1.6568(18) P2−O

2 1.6446(16)

1.6470(13) 1.641(2)

1.6592(13) 1.6599(17)

1.6571(14) 1.6572(14)

1.6590(19) O

1−C2

1.390(3) 1.388(2)

1.386(4) 1.391(2)

1.391(3) 1.390(2)

1.387(3) 1.391(3)

O2−C

6 1.399(3)

1.399(2) 1.403(4)

1.396(2) 1.388(3)

1.388(2) 1.390(3)

1.392(3)

P1−Ni−P2

163.10(3) 162.88(2)

162.95(4) 164.38(2)

163.27(3) 161.58(2)

163.83(3) 163.88(3)

P1−Ni−S1

103.11(3) 103.31(2)

103.03(4) 105.52(2)

104.37(3) 107.50(2)

105.03(2) 91.03(3)

P2−Ni−S1

93.79(3) 93.77(2)

94.02(4) 89.95(2)

92.24(3) 90.02(2)

91.11(2) 105.05(3)

C1−N

i−P1 81.93(7)

81.71(6) 81.77(11)

81.98(6) 81.45(7)

81.50(6) 82.06(7)

81.88(8) C

1−Ni−P2

81.17(7) 81.17(6)

81.19(11) 82.40(6)

82.00(7) 82.03(6)

81.92(7) 82.14(8)

C1−N

i−S1 174.45(7)

174.65(6) 175.00(11)

168.19(6) 173.99(8)

167.87(6) 166.69(7)

166.31(8) C

31−S1−Ni

110.85(8) 111.21(6)

110.95(12) 111.85(7)

114.07(8) 119.93(7)

114.95(7) 115.81(9)


S10

1.0

0.8

0.6

0.4

0.2

0.0

Nor

mal

ized

Rel

ativ

e In

tens

ity

2.0x1051.51.00.50.0Time (s)

Fig. S9 Sample plots of two-parameter fit in KaleidaGraph: kobs for the reaction between [2,6-(Ph2PO)2C6H3]NiSPh (1c) and benzyl bromide ([1c]0 = 0.018 M, [PhCH2Br]0 = 0.18 M) in toluene-d8 at various temperatures (∗: 50°C; : 60°C; : 70°C; : 80°C).

Table S3 kobs for the reaction between [2,6-(Ph2PO)2C6H3]NiSPh (1c) and benzyl bromide in toluene-d8 at

various temperatures.

Temperature [1c]0 (M) [PhCH2Br]0 (M) kobs (s-1) 50 °C 0.018 0.18 1.3(1) × 10-5 50 °C 0.018 0.23 1.7(1) × 10-5 50 °C 0.018 0.28 2.0(1) × 10-5 50 °C 0.018 0.33 2.4(1) × 10-5 60 °C 0.018 0.18 2.2(1) × 10-5 60 °C 0.018 0.23 3.0(1) × 10-5 60 °C 0.018 0.28 3.8(1) × 10-5 60 °C 0.018 0.33 4.3(1) × 10-5 70 °C 0.018 0.18 4.0(2) × 10-5 70 °C 0.018 0.23 5.5(1) × 10-5 70 °C 0.018 0.28 7.0(3) × 10-5 70 °C 0.018 0.33 8.5(2) × 10-5 80°C 0.018 0.18 8.3(4) × 10-5 80°C 0.018 0.23 1.1(1) × 10-4 80°C 0.018 0.30 1.5(1) × 10-4 80°C 0.018 0.33 1.7(1) × 10-4


S11

1.0

0.8

0.6

0.4

0.2

0.0

Nor

mal

ized

Rel

ativ

e In

tens

ity

6x105420Time (s)

Fig. S10 Sample plots of two-parameter fit in KaleidaGraph: kobs for the reaction between [2,6-(Ph2PO)2C6H3]NiSC6H4Z (1a, 1b, 1d, 1e) and benzyl bromide ([1]0 = 0.020 M, [PhCH2Br]0 = 0.20 M) in toluene-d8 at 60 °C (∗: 1e; : 1d; : 1b; : 1a).

Table S4 kobs for the reactions between [2,6-(Ph2PO)2C6H3]NiSC6H4R (1a, 1b, 1d, 1e) and benzyl bromide in toluene-d8 at 60°C.

complex [Ni]0 (M) [PhCH2Br]0 (M) kobs (s-1) 1a 0.015 0.15 4.4(1) × 10-5 1a 0.015 0.20 5.4(1) × 10-5 1a 0.015 0.25 6.3(4) × 10-5 1a 0.015 0.33 8.9(2) × 10-5 1b 0.020 0.20 3.7(2) × 10-5 1b 0.019 0.25 4.1(1) × 10-5 1b 0.015 0.30 5.4(3) × 10-5 1b 0.015 0.35 5.9(1) × 10-5 1d 0.020 0.20 1.0(1) × 10-5 1d 0.020 0.25 1.2(1) × 10-5 1d 0.020 0.30 1.4(1) × 10-5 1d 0.020 0.35 1.7(1) × 10-5 1e 0.020 0.20 3.3(1) × 10-6 1e 0.020 0.25 4.0(1) × 10-6 1e 0.020 0.30 4.8(1) × 10-6 1e 0.020 0.35 5.9(1) × 10-6


S12

2.0x10-4

1.5

1.0

0.5

0.0

k obs

(s-1

)

0.30.20.10.0[PhCH2Br] (M)

Fig. S11 Plots of kobs versus concentration of benzyl bromide for the reaction of [2,6-(Ph2PO)2C6H3]NiSPh (1c) with benzyl bromide in toluene-d8 at various temperatures (: 80°C; : 70°C; : 60°C; ∗: 50°C)

Table S5 Summary of the second-order rate constants k for the reaction of [2,6-(Ph2PO)2C6H3]NiSPh (1c) with benzyl bromide in toluene-d8 at various temperatures.

T (K) 1/T (K-1) k (s-1M-1) ln(k/T) 323 0.00310 7.1(3) × 10-5 -15.33 333 0.00300 1.4(1) × 10-4 -14.68 343 0.00292 2.8(1) × 10-4 -14.02 353 0.00283 5.4(2) × 10-4 -13.39

!

!


S13

-16.0

-15.5

-15.0

-14.5

-14.0

-13.5

-13.0

ln(k

/T)

3.2x10-33.13.02.92.81/T (K-1)

Fig. S12 An Eyring plot for the reaction of [2,6-(Ph2PO)2C6H3]NiSPh (1c) with benzyl bromide in toluene-d8 between 50 °C and 80 °C.

⇒ ΔH‡ = 61.5 ± 0.8 kJ mol-1 and ΔS‡ = −135.1 ± 2.9 J K-1 mol-1

1.0x10-4

0.8

0.6

0.4

0.2

0.0

k obs

(s-1

)

0.40.30.20.10.0[PhCH2Br] (M)

Fig. S13 Plots of kobs versus concentration of benzyl bromide for the reaction of [2,6-(Ph2PO)2C6H3]NiSC6H4Z (1a-e) with benzyl bromide in toluene-d8 at 60 °C (: 1a; : 1b; ∗: 1c; �: 1d; ×: 1e).


S14

Table S6 Summary of second-order rate constants k for the reactions of [2,6-(Ph2PO)2C6H3]NiSC6H4Z (1a-e) with benzyl bromide in toluene-d8 at 60 °C.

Complex 1a 1b 1c 1d 1e k (s-1M-1) 2.5(2) × 10-4 1.6(2) × 10-4 1.4(1) × 10-4 4.4(2) × 10-5 1.7(1) × 10-5

-1.5

-1.0

-0.5

0.0

0.5

1.0

log(

k/k 0

)

0.60.40.20.0-0.2-0.4Substitution constant

Fig. S14 Hammett plot for the second-order rate constants k of the reaction of [2,6-(Ph2PO)2C6H3]NiSC6H4Z (1a-e) with benzyl bromide at in toluene-d8 60 °C.

⇒ ρ= −1.5 ± 0.3

Table S7 kobs for the reactions between {2,6-[(i-Pr)2PO]2C6H3}NiSC6H4Z (2a and 2c) and benzyl bromide in toluene-d8 at 60°C.

complex [Ni]0 (M) [PhCH2Br]0 (M) kobs (s-1) 2a 0.014 0.14 6.0(4) × 10-5 2a 0.014 0.18 8.1(2) × 10-5 2a 0.014 0.21 9.9(4) × 10-5 2a 0.014 0.25 1.1(1) × 10-4 2c 0.014 0.14 2.5(2) × 10-5 2c 0.014 0.18 3.1(4) × 10-5 2c 0.014 0.21 3.6(2) × 10-5 2c 0.014 0.25 4.4(2) × 10-5


S15

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Fig. S15 Plot of kobs versus concentration of benzyl bromide for the reaction of {2,6-[(i-Pr)2PO]2C6H3}NiSC6H4OCH3 (2a) with benzyl bromide in toluene-d8 at 60 °C.!

k = 4.5(5) × 10-4 M-1s-1

50x10-6

40

30

20

10

0

kobs

0.250.200.150.100.050.00[PhCH2Br] (M) !

Fig. S16 Plot of kobs versus concentration of benzyl bromide for the reaction of {2,6-[(i-Pr)2PO]2C6H3}NiSC6H5 (2c) with benzyl bromide in toluene-d8 at 60 °C.!

k = 1.7(1) × 10-4 M-1s-1

!

120x10-6

100

80

60

40

20

0

k obs

0.300.250.200.150.100.050.00[PhCH2Br]


Documents

Substituent Effects on Ni S Bond Dissociation Energies and … · 2012-03-30 · Substituent Effects on Ni−S Bond Dissociation Energies and Kinetic Stability of Nickel Arylthiolate